Hydroxymethylated, fluoroacylated aminohydroxy aromatic compounds



United States Patent 3,352,625 HYDROXYMETHYLATED, FLUOROACYLATEDAMINOHYDROXY AROMATIC COMPOUNDS Domenick Donald Gagliardi, EastGreenwich, RJ., as-

signor to Colgate-Palmolive Company, New York, N .Y.,

a corporation of Delaware No Drawing. Filed Aug. 12, 1963, Ser. No.301,622 3 Claims. (Cl. 8-1163) The present invention relates tohydroxymethylated fiuoroacylated aminohydroxy aromatic compounds to thereaction products of the aforesaid hydroxymethylated aromatic compoundsand substrates having active hydrogen in the surface produced in thepresence of acid catalysts and to solid substrates having attachedthereto the polymers produced by alkaline catalysis of a monomer ofhydroxymethylated fiuoroacylated aminohydroxy aromatic compound.

While man has used woven textiles for raiment for more than two thousandyears, it was not until about one hundred years ago that he sought tomake woven textiles water repellent. The first and, in the light ofrecent knowledge of the basic principles of surface free energy, contactangle and spreading coeificient, unsophisticated water-proofing agentswere various mixtures compounded according to cookbook recipes which,when applied to woven textiles, coated the surface and filled theinterstices of the woven fabric with air-impervious and water-repellentmaterial. This served to provide rainwear such as the Macintosh and thesouwester but was not completely satisfactory for other uses.

In the period 1935 to 1940 in Germany especially at Chemische FabrickePferze with an empirical approach and without understanding the basicprinciples of water repellency, a series of wax emulsions was developedwhich, when padded onto textiles, produced a high contact angle of waterdrops on the surface of the textile and a high degree of showerresistance without changing the porosity or air permeability of thetextile material. The fabrics so treated were not wettable by water orby water-borne stains because of the change in free energy of the fibersurfaces and not because, as in prior art treatments of closing theinterstices of the fabric with deposits of treating material. By the useof the new wax emulsion-metallic salts compositions, it became possibleto produce fabrics which had the feel and appearance of conventionaluntreated fabrics but did not look like oil-clothes, or rubberizedcoated fabrics. The primary practical limitation of such compositionswas and still is the lack of durability to washing and dry cleaning.Products of this type generally comprise a composition containing (a) aparaffin wax or mixtures of vegetable wax esters such as carnauba,candelilla, or sugar cane wax; (b) an emulsifying agent, generally glue,gelatin, and rosin soaps; and (c) an aluminum or zirconium salt, usuallythe formate or acetate. The primary function of the salt is toinsolubilize the glue and other emulsifiers after the emulsion isdeposited on the fabric.

A large variety of such products are still used as lowcost, non-durablewater repellents for textiles. Since neither thermosetting nor fiberreaction occurs with such products, they all are non-durable to washingand dry cleaning. Other than water repellency for rainwear fabrics, suchproducts produce fabrics which have a fair degree of spot-and-stainresistance to water-borne stains.

The search for durable or permanent water-repellent finishing materialsespecially for cellulosic fibers was initiated because of thedeficiencies of the afore-discussed wax emulsions. The first majorimproved product Was offered in England under the trade name of Velan.Velan was octadecyloxymethyl pyridiniurn chloride, a quaternary ammoniumcompound made by the chloromethylation of 3,352,625 Patented Nov. 14,1967 having a composition corresponding to the formula:

This structure, unlike other quaternary ammonium compounds, is unstableand under acid conditions reacts with surfaces containing activehydrogen, e.g., the hydrogen of a hydroxyl group in cellulose fibers. IfZ be the core of the cellulose fiber and OH be an hydroxyl group in thesurface thereof, then the reaction can be represented by the formula:

Fabrics treated with a compound such as Velan are durably waterrepellent, are porous, soft, and appear like untreated fabrics.

Du Pont and Warwick Chemical Co. produced a prodnot which was a majorimprovement of Velan. The improved product was the stearamidomethylanalog of Velan having a composition corresponding to the formula:

C nHaaC ONHCHQN C which is available commercially as Zelan and Norane R.The advantage of the stearamide product is greater initial waterrepellency and greater durability to washing. Such products are leadersin rainwear fabric finishes.

In the search for other fiber reactive or durable water repellents,other classes of materials have now evolved as represented by siliconewater repellents, methylol stearamide compositions (Permel, Ahcovel NW),hydrophobic resin (Norane GG, Ranedare R, Argus DW octadecylketene dimer(Aquapel), and others.

While durable water-repellent finishes had been initially developed forouterwearand rainwear-type applications, in the period 1950 to 1956 suchproducts began to be used widely on mens suitings, dress goods, andupholstery materials. In this exploitation of these finishes emphasiswas placed not on water repellency but on resistance to spotting andstaining by waterborne stains. This use continues. It had been observedthat fabrics treated with such durable water repellents had a highdegree of resistance to soiling by water-borne soils and stains and wereeasier to launder. The principal limitation of such finishes was thatthey attracted rather than repelled oily soils and the fabrics were notrepellent to staining by oil materials such as oils, greases, gravy,mayonnaise, etc.

In the early part of the decade of 1950 to 1960 based on work done atthe Naval Research Laboratory by Fox and Zisman and work done by theKellogg division, later to become a part of the operations of MinnesotaMining and Manufacturing Company, the latter announced the utility ofcertain fluorocarbon based chemicals as finishes for various fibers. Foxand Zisman had demonstrated the physicochemical principle of lowfreeenergy surfaces and the relation to non-wetting with water and oilof surfaces treated with chemicals containing perfluoroalkyl groups.

J The practical developments of Minnesota Mining and ManufacturingCompany resulted in the first product directed to textile finishing.This was and still is the product known as FC-l49. FC-149 is a classicalWerner complex of a carboxylic acid made by reacting one mol of thecarboxylic acid with 2 mols of basic chromic chloride to obtain areaction product having a composition represented by the formula: $9539H The compound is water soluble and cationic in nature. It shows strongadhesion to anionic substrates such as cellulose and fiberglass. It alsocomplexes with proteinaceous materials such as wool, silk, and leatherto yield both waterand oil-repellent surfaces.

A second general class of products developed by Minnesota Mining andManufacturing Company (often referred to as 3M) comprise latices ofperfiuorochemicals.

For example, some of these are believed to have a compositioncorresponding to the formulae:

CH2CH- OO(CHz) -IIISO3-(CF2)nCF3 R These various products made availableby 3M pro .duced a great practical improvement in fabric finishes.

Although of some merit for plain water repellency for outerwearfinishing, the two products offered a solution to obtaining water andoil repellency and practical resistance to staining. Because of itshydrolytic instability, the Werner complex product has been limited towool, leather, and upholstery finishes. The acrylate products havebecome prominent in finishing cotton, rayon, and synthetic fibers.

Thus, while the progress in the art of imparting Water- .repellency totextiles has been noteworthy, the'soiling problem has not been solved.Recognizing the need for reproducible results, those concerned withresearch in this field have developed a test for water repellency, atest for oil repellency, a test for resistance to water-borne andoil-borne stains and, for household furnishings, the most important: atest to evaluate particulate soil repellency.

Water repellency.Resistance to wetting (spray test) AA T CC StandardTest Method 221952 This test method is applicable to any textile fabric.It measures the resistance of fabrics to wetting by a water spray, andthe results depend primarily on the degree of hydrophobicity inherent inthe fibers and yarns and subsequent treatments applied. Water is sprayedagainst the taut surface of a test specimen. Evaluation of the wettedpattern is readily brought about by comparing the wetted pattern withstandard wetting-pattern pictures.

When measuring the spray rating, especially of finishes of the presentinvention, it is not unusual to encounter a test specimen withsufiicient hydrophobic properties to confine the area of wetting and yetpermit wetting through. Thus, it becomes necessary to have a rating forthis condition. The following illustrates this modification of thestandard wetting evaluation:

A spray rating number of 70/0 is reported for a spray pattern comparableto the standard 70 rating but the under surface is also wetted to someextent. The 70 of the numerator indicates equivalence with the standardtest pattern for a rating of 70. The zero in the denominator indicateswetting to the under surface of the cloth at the wet areas.

The test specimens having a minimum size ,of 7" x 7" are conditioned at70 F. and 65 percent relative humidity for a minimum of four hoursbefore testing. The test specimen, fastened securely and wrinkle free ina metal hoop having a diameter of 6 inches, is placed and centered 6inches under a standard spray nozzle at an angle of 45 degrees to thehorizontal. Two hundred and fifty milliliters of water at i2 F. ispoured into the funnel attached above the spray nozzle. The spray laststwenty-five to thirty seconds at the end of which time the hoop is takenby one edge and the opposite edge tapped smartly once against a solidobject with the wet side facing the solid; this procedure is repeatedwith the hoop reversed 180 degrees.

Oil repellency tests.3M oil repellency test: 3M Textile Chemicals(Appendix A, Test Methods, page 1) Oil Repellency Percent HeptanePercent Nujol Rating by Volume by olume 1 No hold out to Nujol.

The standard oil-heptane mixtures are contained in small stopperedmedicine dropper bottles. A drop of each mixture is placed on thefabric. The appearance of the test oil is observed through the drop.Note is made whether wetting or penetration has occurred. The numbercorresponding to that mixture containing the highest percentage ofheptane which does not penetrate nor wet the fabric after three minutesis considered the oil repellency rating of the system.

The change in the optical refractivity of the drop is often anindication of wetting. In some cases wetting can be better determined byobserving the other side of the fabric. In some cases of zerooil/heptane rating, the symbol 0+ has been used to indicate a modicum ofresistance to wetting by oil.

Stain Repellency.Standing tests in anti-soiling evaluation of theresistance of textile fabrics to waterand oil-borne stains frames. Allor part of the frame area is useddepending" Appearance Rating No visiblestain 5 Slight stain 4 Easily noticeable stain 3 Considerable stain 2Very heavily stained 1 (The spread or lack of spread is not necessarilyreflected in these ratings.)

(d) Duplicate sets of stains are applied in separate areas so thatone-half of the fabric can be washed. In most instances, the washing iscarried out with 50 grams of FAB, in a cotton cycle, and a dummy load tototal 5 pounds in a Norge Home Automatic Washer.

The following two lists describe the numbering system and organizationof the stains on the fabrics:

Oil stains (6) Wesson Oil (7) Gulf Supreme Motor oil 20/20 (8)Oleomargarine b Water stains (1) instant tea a (2) Sheaifers 232blueblack Skrip (3) A & P Concord grape juice (9) La Rosa to m at o (4)Ann Page salad mnssauce tard (l) Jergens lotion Bosco chocolate syrupEight cubic centimeters of dry powder per 200 cubic centimeters of waterapplied at 160 F.

b Melted and applied at 160 F.

Those skilled in the art will recognize that, while these stains are notscientifically compounded, they are stains to which householdfurnishings are exposed in the use attendant upon everyday life.

When reporting the relative resistance to staining and relative ease ofremoving stain in laundering, the values from water-borne stains andoil-borne stains are averaged and reported. In all cases the stains areallowed to dry on the fabrics for twenty-four hours before washing.

Household furnishings is a term used herein to designate all articles inthe home of prince or pauper which are washed regularly at relativelyfrequent intervals or semioccasionally at relatively irregularinfrequent intervals. Household furnishings include bed linen, i.e.,sheets, pillow cases, blankets, tablecloths, napkins, curtains,draperies, nnderthings, shirts, dresses, sox, handkerchiefs, blouses,skirts, slipcovers, and the like. It will be recognized that the termhousehold furnishings is inclusive but not exclusive.

As everyone will recognize while the aforedescribed controlled stainingtests are extremely useful for evaluating the effectiveness of varioustextile finishes, the incidence of staining a shirt front with salad oil(Wesson Oil) is only occasional whereas the staining of the collar andends of a mans shirt with the finely divided soil of the environmentmixed with the oily exudations of the healthy human skin is amoment-to-moment occurrence. Hence, important as the aforedescribedtests are, a test to evaluate the resistance of a finish to the pickupof such soil, hereinafter designated oily particulate soil, i.e., a testto evaluate the ability to shed oily particulate soil and the ease withwhich such oily particulate soil is removed by laundering undercontrolled conditions of soiling is of greater importance. Such acontrolled test providing reproducible results has been developed and isdesignated the GRC Dry Soil Test.

GRC Dry Soil Test Fifteen to twenty 6" x 8" numbered specimens (usuallyx 80 cotton), including at least one untreated control, are tumbled forthirty minutes with 10 percent Cyanamid Soil based on the weight of thefabric. The tumbling is carried out in a 5-liter capacity Five MinuteHome Cleaner at 44 'r.p.m.; six No. 8 Neoprene r-ubber stoppers aredistributed among the specimens to increase the mechanical action. Atthe end of the tumbling, the specimens are removed and each shaken upand down separately fifteen times by hand to remove surface dirt.

The specimens are then cut in two to produce two 4" x 6 pieces. One-halfis washed with 50 grams of FAB in a cotton cycle with a S-pound dummyload, then hung to dry, and lightly ironed under a clean cotton cloth.

The degree of soil is determined with the Photovolt Reflectance Meter(Tri-Blue Filter). Six readings per specimen are taken. The average ofthe six readings is reported.

Cyanamid Soil The American Cyanamid Synthetic Soil described below isalso recommended by the Minnesota Mining and Manufacturing Company. Thedry ingredients are blended thoroughly, dried in a forced draftconvection oven for eight hours at 50 C., then milled twenty-five hourswith ceramic balls and stored in a polyethylene bag.

Material: Percent by weight Peat moss 38 Cement l7 Kaolin clay 1 17Silica200 mesh 17 Furnace black 1.75 Red iron oxide 0.50

Mineral oil 8.75

1R. T. Vanderbilt Peerless.

2 Davisou Chemical Company,

3 Benny '& Smith Co. Molacco.

4 C. K. Williams C0.

It has been found that hydroxymethylated, fluoroacylated derivatives ofaminohydroxy aromatic compounds having at least two active nuclearhydrogens impart to confer upon or endow textiles, i.e., fibers, yarns,fabrics, and the like composed of cellulosic, including natural such ascotton and regenerated proteinaceous including natural such as wool andsynthetic fiber and particularly fibers having active hydrogen in thesurface. It is to be observed that the compounds of the presentinvention can also be used for coating materials which do not haveactive hydrogen in the surface such as the polyal'kylenes, e.g.,polypropylene, and metals such as steel.

In general, the compounds of the present invention are prepared bymethods of classical chemistry. Thus, an aromatic compound having onebenzene ring or two or more fused rings is reacted in known manner toobtain the hydroxy compound. The latter is then reacted in known mannerto obtain the amino hydroxy compound. Vfhile the single ring compoundsare limited to a single amino and a single hydroxy group, i.e.,paraaminophenol having two active nuclear hy-drogens, the aromaticcompounds having two or more fused rings can have one or a plurality ofhydroxy groups and one or a plurality of amino groups provided theresulting compound has two active nuclear hydrogens. Thus, for example,the dimethylol derivative of paraaminophenol is illustrative of thesingle ring compounds while aminoalphanaphthol or 4-aminonaphthol isillustrative of the m-ulti-ring compounds which can be used as startingmaterials for the preparation of the mono-methylol or dimethylolcompounds of the present invention.

Illustrative of the preparation of a perfiuoroacyl derivative ofparaaminophenol having the generic formula:

C -C ll HOG CNHCQ C=C H H where Q is an alkyl group having '3 to 21carbon atoms in which at least 7 0 percent of the to 43 hydrogen atomshas been replaced with fluorine atoms and the terminal, i.e., omegacarbon atom has at least two and preferably three fluorine atoms.

Thus, 0.1 mol of the butyl ester of perfluorooctanoic acid H 0 F3 0 Fy-,0 0 GHZCHZCZH5 is mixed with 0.1 mol of p-aminophenol, NH C H OH, and225 parts by weight of methyl ethyl ketone. The reaction mixture washeated to reflux temperature (80 C.)

for 3.5 hours to eifect ammo-nolysis. The reaction can' be representedby the equation:

While the reaction represented by Equation 3 involves the reaction ofthe perfiuoroacyl-p-aminophenol with formaldehyde in the molal ratio ofl to 2, those skilled in the art will understand that theperfiuoroacyl-p-aminophenol can be reacted with formaldehyde in themolal ratio of 1 to 1. Accordingly, the methylol derivatives ofperfluoroacylaminohydroxy aromatic compounds having two active hydrogenshave the generic formula:

where R is the nucleus of an aminohydroxy aromatic compound having asingle ring, two fused rings, or three fused rings, Q has the samesignificance as in Formula 1, R is hydrogen or alkyl having one to fivecarbon atoms, n is 1 or 2, m is one or two, t is one or two, s aninteger 6, 8, or 10 minus (m+n+t), x is the same as t.

The novel perfluoroacyl aminohydroxy monomethylol and dimethylolcompounds are not to be confused with prior disclosed compounds assimple methylol phenols. For example, in U.S. Patent No. 2,468,530, theafter treatment of viscose rayon to reduce the swelling value andincreasing the water resistance and wet strength of viscose rayon withmonoand di-substituted derivatives of monoand (ii-substituted phenolssuch as paracresol monoand di-alcohols represented by the formula:

where R is H or CH OH. However, these resins do not confer surface wateror oil repellency to textile fibers.

The perfiuoroacyl derivatives of aminohydroxy aromatic compounds are notto be confused with the perfluorinated cyclohexyl carboxylic acid andcyclohexyl acetic acid derivatives described in U.S. Patent No.2,593,737 having the composition represented by the generic formula R-Zwhere R is a saturated polycarbon fluorocarbon radical containing atleast three carbon atoms and Z is a monocarboxyl radical or acarbon-containing derivative radical hydrolyzable thereto such as C FCOOH, undecafiuorocyclohexyl carboxylic acid.

In U.S. Patent No. 2,495,239 a method for treating cellulose isdescribed. The patented method comprises condensing in alkaline mediumpara-tertiary-amyl phenol and formaldehyde in the molecular ratio of 1:2and reacting the condensation product with cellulose material containingfree hydroxyl groups and subjecting the cellulosic reaction products tothermal treatment to form resiniform bridge linkages between thecellulose chains.

A process of rendering textile fabrics, yarns, and fi-bers Waterproofwithout materially altering the general appearance of the fabric isdescribed in U.S. Patent No. 2,257,088. These results are produced bythe use of compounds having the general structure in which Ar representsan aromatic nucleus of the benzene or naphthalene series carrying anuclearly bound oxygen and at least one hydrocarbon substituent of thealiphatic or cycloaliphatic series which contains eight or more carbonatoms and which is bound to the aromatic nucleus directly or through anether, carbonyl, carboxyl, or carbamido linkage. The nuclearly boundoxygen may be part of hydroxyl group or a part of a side chain. A and Brepresent members of the group consisting of open chain, lower aliphaticgroups when taken singly and when taken together divalent groups whichjointly with the nitrogen form a heterocycle.

In direct contrast to the materials described in the foregoing U.S.patents, the compounds of the present invention are high melting pointwaxes which either react with active hydrogen in the substrate in thepresence of an acid catalyst such as oxalic, phosphoric, and zincnitrate, or form a coating on the substrate be it fibrous such ascotton, wool, nylon, polyethylene, wood, steel, aluminum, glass, orother ceramic having no active hydrogen when an alkaline catalyst suchas NaOH, borax, and potassium methoxide is used.

Thus, for example, the dirnethylol perfiuorooctanoylaminophenol, thepreparation of which has been described hereinbefore, can be suspendedin water containing an acid catalyst, a fibrous material immersed in thewater, the treated fibrous material squeezed to at least percent wetpick-up and the treated fibrous material heattreated at a temperature inthe range of 250 to 300 F. for a period of time inversely proportionalto the temperature and for example five to ten minutes at 300 F. (80percent wet pick-up is a term meaning that the fibrous material contains80 percent by weight based on the weight of the fibrous material of theaqueous suspension. Hence, when the suspension contains 1 percent byweight of the methylol derivative, the fibrous material contains 0.8percent of the methylol derivative. Similarly, the methylol derivativecan be dissolved in a suitable solvent, for example, xylene containingan acid catalyst, the fibrous material immersed in the solution of themethylol derivative, the fibrous material squeezed to the predeterminedwet pick-up in the fibrous material, the solvent removed and the treatedfibrous material heat treated as previously described.

On the other hand, any solid substrate with or without active hydrogencan be treated to provide the solid substrate with a coating of thepolymerized methylol derivative. Thus, an aqueous suspension or asolution in a suitable organic solvent such as xylene cotaining analkaline catalyst for example NaOCH ZnO, and triethanolamine can beapplied to the solid substrate in any suitable manner as by dipping,spraying, spreading, or other means, the excess, if any, removed, andthe treated solid substrate heat treated at elevated temperatures of atleast 250 F. but below the decomposition temperature of the substrate orthe methylol polymer for a period of time inversely proportional to thetemperature, for example, at 300 F. for five to ten minutes.

Indicative of the waterand oil-repellency and the resistance to soilingby oily particulate soil is the treatment of cotton with thebis-formaldehyde adduct to perfluorooctanoyl-p-aminophenol:

where Q is Treatment applied-3 product plus 0.5% Zn(NO .6H O

Oil repellency obtained Reflectance:

Before wash 33 After wash 62 Accordingly, the present invention provides(1) novel monoand di-methylolamino hydroxy aromatic compounds, (2)fibrous or solid substrates having associated therewith polymerizedmonoand di-methylol aminohydroxy aromatic compounds, and (3)perfiuoroacyl aminohydroxy aromatic compounds.

What is claimed is:

1. The reaction product produced by the acid catalyzed reaction of anfibrous substrate having active hydrogen in the surface therewith with amethylolperfiuoroacylaminohydroxy aromatic reactant, corresponding tothe formula:

NORMAN G. TORCHIN, Primary Examiner.

I. C. CANNON, Assistant Examiner.

1. THE REACTION PRODUCT PRODUCED BY THE ACID CATALYZED REACTION OF ANFIBROUS SUBSTRATE HAVING ACTIVE HYDROGEN IN THE SURFACE THEREWITH AMETHYLOPERFLUOROACYLAMINOHYDROXY AROMATIC REACTANT, CORRESPONDING TO THEFORMULA: